CN109153578A - High silicon AFX framework-type molecular sieve - Google Patents

High silicon AFX framework-type molecular sieve Download PDF

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Publication number
CN109153578A
CN109153578A CN201780029447.3A CN201780029447A CN109153578A CN 109153578 A CN109153578 A CN 109153578A CN 201780029447 A CN201780029447 A CN 201780029447A CN 109153578 A CN109153578 A CN 109153578A
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sio
type zeolite
zeolite
framework
afx
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T·M·达维斯
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Chevron USA Inc
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/8625—Nitrogen oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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    • B01D53/9404—Removing only nitrogen compounds
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    • B01D53/9413—Processes characterised by a specific catalyst
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
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    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/00—Catalysts
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    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Abstract

Disclose a kind of SiO2/Al2O3Molar ratio is greater than 50 AFX Framework-type zeolite.High silicon AFX Framework-type zeolite is to be synthesized in the presence of the Organic structure directing agent for containing bis- (1- adamantyl) glyoxaline cations of 1,3- by the reaction mixture with high silicon dioxide and low hydrogen oxide concentration.

Description

High silicon AFX framework-type molecular sieve
Technical field
The present disclosure relates generally to have the SiO greater than 50 to 1002/Al2O3The AFX Framework-type zeolite of molar ratio, synthesis, As well as the purposes of adsorbent and catalyst.
Background
Verified natural and synthesis of molecular sieve material (for example, zeolite, aluminate or phosphate or mesopore material) is for various types of The hydrocarbon conversion of type has catalytic property, and is used for many industrial process.These materials are characterized in that orderly porous crystalline Structure, the structure can be determined by X-ray diffraction (XRD).Since the hole of these materials has molecular dimension, selection Property the absorption of unique size be it is possible, hence obtain one's name " molecular sieve ".
Molecular sieve is classified according to the rule of the IUPAC Zeolite Nomenclature committee by the structure committee of International Zeolite Association.According to The classification, the framework-type zeolite and other crystalline microporous moleculars for having been set up structure, which sieve, to be assigned three-letter codes and retouches It is set forth in " Atlas of Zeolite Framework Types " the 6th revised edition, Elsevier, 2007.
It is known for being accredited as the molecular sieve with framework types AFX by the structure committee of International Zeolite Association.AFX skeleton One example of types of material is zeolite SSZ-16.
United States Patent (USP) No.4,508,837 discloses zeolite SSZ-16 and its derived from (the 1- azabicyclo of 1,4- bis- [2.2.2] octane) lower paraffin hydrocarbon nitrogen-containing organic compound in the presence of preparation, wherein the nitrogen-containing organic compound is rudimentary Paraffin section has 3-5 carbon atom.
United States Patent (USP) No.5,194,235 is disclosed using DABCO-Cn- two quaternary ammonium Organic structure directing agents prepare zeolite The method of SSZ-16, wherein n is 3,4 or 5.It is reported that prepared SSZ-16 zeolite SiO2/Al2O3Molar ratio usually 8 to In the range of 15.
Lobo et al. (Chem.Mater.1996,8,2409-2411) reports zeolite SSZ-16 can only be in the SiO of limitation 2 SiO2/Al2O3Synthesis in molar ratio range.
United States Patent (USP) No.8,562,942 is disclosed to be synthesized in the presence of 1,3- bis- (1- adamantyl) glyoxaline cations AFX Framework-type zeolite, wherein reaction mixture SiO2/Al2O3Molar ratio is 35, and hydroxide/silica molar ratios are 0.05.In higher SiO2/Al2O3Under molar ratio (such as 50 or 100), the material in addition to AFX Framework-type zeolite is produced.
U.S. Patent Application Publication No.2016/0137518, which is disclosed, has at least 90% mutually pure AFX skeleton and SiO2/ Al2O3The aluminosilicate zeolite that molar ratio is 12 to 50.
According to the disclosure, SiO is disclosed2/Al2O3Molar ratio is greater than 50 to 100 AFX aluminosilicate zeolites.
It summarizes
In one aspect, a kind of AFX Framework-type zeolite is provided, the zeolite has under form after its calcining is greater than 50 To 100 SiO2/Al2O3Molar ratio.
On the other hand, a kind of AFX Framework-type zeolite, the zeolite original sample and anhydrous form after its synthesis are provided Under, have with the consisting of of molar ratio computing:
Usable levels Representative value
SiO2/Al2O3 > 50 to 100 > 50 to 80
Q/SiO2 > 0 to 0.1 > 0 to 0.1
M/SiO2 > 0 to 0.1 > 0 to 0.1
Wherein Q includes bis- (1- adamantyl) glyoxaline cations of 1,3-, and M is the gold selected from periodic table the 1st race and the 2nd race Belong to.
On the other hand, a kind of SiO for synthesizing and having greater than 50 to 100 is provided2/Al2O3The AFX matrix type of molar ratio The method of zeolite, which comprises (a) provides the reaction mixture including following substance: (1) including FAU Framework-type zeolite Silicon source；(2) individual silicon source；(3) it is selected from source at least one metal (M) of the 1st race of the periodic table of elements and the 2nd race；(4)1,3- The source bis- (1- adamantyls) glyoxaline cation (Q)；(5) hydroxide ion；(6) water；And (b) make the reaction mixture Be subjected to being enough to be formed the crystallization condition of AFX Framework-type zeolite crystal, wherein the reaction mixture have with molar ratio computing as Lower composition:
SiO2/Al2O3 > 50 to 100
M/SiO2 0.05 to 0.25
Q/SiO2 0.10 to 0.30
OH/SiO2 0.15 to 0.55
H2O/SiO2 15 to 60
It yet still another aspect, provide it is a kind of for by include organic compound the raw material method that is converted to converted product, The method includes contacting raw material and catalyst under the conditions of organic compound conversions, the catalyst includes this hair The active form of bright AFX framework type molecular sieve.
It yet still another aspect, providing a kind of method for being used for selective reducing nitrogen oxide (NOx), the method includes making Air-flow containing NOx is contacted with catalyst, and the catalyst includes the active form of AFX framework type molecular sieve of the present invention.
It is described in detail
It introduces
Unless otherwise indicated, following term will throughout the specification using and have following meanings.
Term " zeolite " refers to crystal aluminosilicate composition, is micropore and the AlO by corner-sharing2And SiO2On four sides Body is formed.
Term " framework types " is at " Atlas of Zeolite Framework Types ", the 6th revised edition, Elsevier, meaning described in 2007 use.
Terms used herein " after synthesis as former state " refer to before removing Organic structure directing agent, its form after crystallizing Zeolite.
Terms used herein " anhydrous " refer to the zeolite substantially free of physical absorption and chemical absorbed water.
As it is used herein, the numbering plan of periodic table of elements race such as Chem.Eng.News, 63 (5), 27 (1985) institutes As open.
Reaction mixture
In general, AFX Framework-type zeolite of the invention is prepared by the following method: (a) providing the reaction including following substance Mixture: (1) include FAU Framework-type zeolite silicon source；(2) individual silicon source；(3) the 1st race of the periodic table of elements and the 2nd race are selected from The source at least one metal (M)；(4) source 1,3- bis- (1- adamantyls) glyoxaline cation (Q)；(5) hydroxide ion；With (6) water；And the reaction mixture (b) is made to be subjected to being enough to be formed the crystallization condition of AFX Framework-type zeolite crystal,
The reaction mixture for forming AFX Framework-type zeolite is listed in table 1 below with forming for molar ratio computing:
Table 1
Reactant Usable levels Representative value
SiO2/Al2O3 > 50 to 100 60 to 95
M/SiO2 0.05 to 0.25 0.05 to 0.10
Q/SiO2 0.10 to 0.30 0.10 to 0.17
OH/SiO2 0.15 to 0.55 0.15 to 0.27
H2O/SiO2 15 to 60 20 to 50
Wherein composition variable M and Q are as described above.
Suitable FAU Framework-type zeolite can from such as Zeolyst International (Conshohocken, PA) and Tosoh Corporation (Tokyo, Japan) is obtained.
The SiO of FAU Framework-type zeolite2/Al2O3Molar ratio can be for 5 to 100 (for example, 5 to 80,5 to 60,5 to 30,10 To 100,10 to 80,10 to 60 or 10 to 30).
In addition to FAU Framework-type zeolite, suitable silicon source includes hydrated alumina and water-soluble aluminum salt (such as aluminum nitrate).
Suitable silicon source include colloidal silicon dioxide, pyrogenic silica, precipitated silica, alkali silicate and Orthosilicic acid tetraalkyl ester.
The example of suitable 1st race or group II metal (M) includes sodium, potassium and calcium, preferably sodium.Metal (M) is usually as hydrogen Oxide is present in reaction mixture.
AFX Framework-type zeolite of the invention is that have using comprising 1,3- bis- (1- adamantyl) glyoxaline cation (Q) The synthesis of machine structure directing agent, described to be indicated by bis- (1- adamantyl) glyoxaline cations (Q) of 1,3- with flowering structure (1):
The suitable source Q is hydroxide, chloride, bromide and/or other salt of quaternary ammonium compound.
Reaction mixture also contains hydroxyl ion source, such as the 1st race's metal hydroxides, such as sodium hydroxide or hydroxide Potassium.The counter ion that hydroxide can also be used as Organic structure directing agent exists.
Reaction mixture is also containing the crystal seed of molecular screen material, ideal such as from previously synthesized SSZ-16 zeolite Amount be 0.01 to 10, the 000ppm weight (for example, 100 to 5000ppm weight) based on reaction mixture.
For each embodiment as described herein, zeolite reaction mixture can be supplied by more than one source.Moreover, Two or more reactive components can be provided by a kind of source.
Reaction mixture can be prepared in batches or continuously.Crystalline size, form and the crystallization time of zeolite described herein It can change with the property and crystallization condition of reaction mixture.
Crystallization and synthesis post-processing
The crystallization of zeolite from above-mentioned reaction mixture can suitably react under static, overturning or stirring condition It is carried out in device container, such as polypropylene tank or teflon lining or stainless steel autoclave, temperature is to protect from 125 ° at 200 DEG C It holds the time for being enough to crystallize at the temperatures used, such as 5 days to 30 days.Crystallization usually carries out at autogenous pressures.
Zeolite crystal once being formed is mixed solid product from reaction as being centrifuged or filtering by standard mechanical separation techniques Object recycling.Crystal is washed, is then dried to obtain the zeolite crystal of synthesis.Drying steps are usually being lower than 200 DEG C of temperature Lower progress.
As crystallization process as a result, the crystalline molecular sieve product of recycling is closing in its pore structure containing at least part The structure directing agent used in.
The zeolite of original sample after synthesis can be handled, to remove part or all of organic structure used in its synthesis Directed agents.This can easily be carried out by heat treatment (calcining), wherein by the material of original sample after synthesis at least about 370 DEG C At a temperature of heat at least 1 minute and usually no longer than 20 hours.Heat treatment can up to 925 DEG C at a temperature of carry out.Although It can be heat-treated using the pressure lower than normal pressure, but need normal pressure for convenience's sake.It additionally or alternatively, can be with By removing Organic structure directing agent (see, e.g., A.N.Parikh etc., Micropor.Mesopor.Mate with ozone treatment r.2004,76,17-22).Product without organic matter, especially its metal, hydrogen and ammonium form, especially suitable for certain organic (examples Such as hydrocarbon) catalysis of conversion reaction.In the present invention, " active form " for being referred to as zeolite without organic matter zeolite of hydrogen form, is deposited Or be not present metal function, such as Pt or Pd.
According to required degree, outer 1st race of skeleton or group II metal cation in AFX Framework-type zeolite of the present invention can According to technology well known in the art by being replaced with the ion exchange of other cations.It is suitable that cation is replaced to include gold Belong to ion, hydrogen ion, hydrogen precursor ion (such as ammonium ion) and combinations thereof.It is preferred that cation is replaced to be that those customization catalysis are lived The cation for certain chemical conversion reactions of property.Particularly preferred substitution cation includes hydrogen, rare earth metal and element week The metal of phase Biao 2-15 race.
When used as a catalyst, it may be desirable to will be used in AFX Framework-type zeolite of the present invention and tolerance organic conversion processes Temperature and the materials of other conditions be combined together.Such material include activity and inert material, and synthesis, it is naturally occurring Zeolite and inorganic material, such as clay, silica and/or metal oxide, such as aluminium oxide.The latter can be natural The form of the colloid of existing or gelatinous precipitate or the mixture including silica and metal oxide.By material and this hair (i.e. in combination during the synthesis of new crystal or presence) is used in combination in bright AFX Framework-type zeolite (to be active) has certain Often change the conversion ratio and/or selectivity of catalyst in machine conversion process.Inert material suitably serves as diluent to control The amount converted during given is made, so as to obtain product in economic and orderly mode, and is not had to anti-using control Answer other means of rate.These materials can be coupled to naturally occurring clay (such as bentonite and kaolin), to improve Crushing strength of the catalyst under commercial operating conditions.The material (that is, clay, oxide etc.), plays for catalyst The effect of adhesive.It is intended to provide the catalyst with good crushing strength, because in business in use, wishing to prevent catalyst It is fragmented into dusty material.These clays and/or oxide adhesive are typically only used for improving the mesh of the crushing strength of catalyst 's.
Naturally occurring clay that can be compound with AFX Framework-type zeolite of the present invention includes that montmorillonite and kaolin are serial, The series includes sub-Ben (sub-bentonite) and well known kaolin, such as Dixie, McNamee, Georgia and Florida clay or in which main mineral constituent are the other viscous of halloysite, kaolinite, dickite, nacrite or anauxite Soil.Such clay can be calcined with original exploitation or initially, acid is handled or the raw material form of chemical modification uses.It can be used for Compound adhesive further includes inorganic oxide with AFX Framework-type zeolite of the present invention, for example, silica, zirconium oxide, titanium oxide, Magnesia, beryllium oxide, aluminium oxide and their mixture.
In addition to previous materials, AFX Framework-type zeolite of the present invention can also be compound with porous matrix material, such as titanium dioxide Silicon-aluminium oxide, silica-magnesia, silica-zirconium oxide, silica-thorium oxide, silica-beryllia, two Silica-titania and ternary composition, such as silica-alumina-thoria, silica-alumina-oxidation Zirconium, silica-alumina magnesia and silica-magnesiazirconia.
The relative scale of AFX Framework-type zeolite and inorganic oxide matrix of the present invention may vary broadly, wherein the present invention AFX Framework-type zeolite content range is the 1-90 weight % (for example, 2-80 weight %) of composition.
The characterization of zeolite
After its synthesis as former state and under anhydrous form, AFX Framework-type zeolite of the present invention has with molar ratio computing such as the following table 2 Shown in chemical composition:
Table 2
Usable levels Representative value
SiO2/Al2O3 > 50 to 100 > 50 to 80
Q/SiO2 > 0 to 0.1 > 0 to 0.1
M/SiO2 > 0 to 0.1 > 0 to 0.1
Wherein Q includes bis- (1- adamantyl) glyoxaline cations of 1,3-, and M is the gold selected from periodic table the 1st race and the 2nd race Belong to.
In some embodiments, AFX Framework-type zeolite of the invention has as former state and under anhydrous form after its synthesis SiO in the range of being greater than 50 to 902/Al2O3Molar ratio (for example, > 50 to 70,52 to 90,52 to 80,52 to 70,53 to 90,53 to 80,53 to 70,55 to 90,55 to 80 or 55 to 70).
It should be noted that intact form can have and be used to prepare after the synthesis of AFX Framework-type zeolite of the invention The different molar ratio of the molar ratio of the reactant of the reaction mixture of intact form after synthesis.The result may be due to not 100% reactant is fully introduced into the crystal of formation (from reaction mixture).
Under its calcinated form, AFX Framework-type zeolite of the invention has the chemical composition comprising following molar relationship:
Al2O3:(n)SiO2
Wherein the value of n be greater than 50 to 100 (for example, > 50 to 90, > 50 to 80, > 50 to 70,52 to 100,52 to 90,52 to 80,52 to 70,53 to 100,53 to 90,53 to 80,53 to 70,55 to 100,55 to 90,55 to 80 or 55 to 70).
High silicon dioxide AFX Framework-type zeolite of the invention is characterized in that powder x-ray diffraction.Represent AFX skeleton class The XRD diagram of type zeolite may refer to Collection of Simulated XRD Powder Patterns for Molecular Sieves ", the 5th revised edition, Elsevier, 2007.Minor change in diffraction pattern is attributed to lattice constant Change, may be caused by the variation of the molar ratio of the skeleton type of specific sample.In addition, sufficiently small crystal will affect peak Shape and intensity lead to significant peak broadening.Minor change in diffraction pattern can organise as used in preparation process It closes the variation of object and causes.Calcining may also lead to the minor shifts in X-ray diffractogram.In spite of these small disturbances, but Elementary cell structure remains unchanged.
Using method described herein, the high silicon dioxide AFX matrix type boiling substantially free of non-AFX material can be synthesized Stone.Terms used herein " substantially free of non-AFX material " refer to that AFX Framework-type zeolite of the invention contains less than 5 weights The non-AFX material for measuring % (for example, less than 2.5 weight %, less than 1 weight % or immeasurablel amount), passes through conventional XRD skill Art measurement.The example of this non-AFX material includes amorphous materials, unreacted FAU Framework-type zeolite and the boiling of CHA matrix type Stone.Non- AFX material can be mixed with AFX material cocrystallization or with AFX material.
Absorption and catalysis
AFX Framework-type zeolite of the invention can be used as adsorbent.For example, it may be used as selective absorbent, being used for will First component (such as CO2) separated from the admixture of gas comprising the first component and other the second component (such as methane).
AFX Framework-type zeolite of the invention can be used for being catalyzed a variety of chemical conversion process, especially organic compound (such as Hydrocarbon) conversion process.By the material itself or with one or more other catalytic active substance (including other crystalline catalysts) groups The example for closing the chemical conversion process being effectively catalyzed includes needing to have those of catalyst of acid activity.
AFX Framework-type zeolite of the invention can be suitable as oxygenate conversion at one or more alkene, especially The catalyst of ethylene and propylene.Term " oxygenatedchemicals " herein for including aliphatic alcohol, ether, carbonyls (aldehyde, Ketone, carboxylic acid, carbonic ester etc.), and contain heteroatomic compound, such as halide, mercaptan, sulfide, amine and combinations thereof.Rouge Race part usually contains 1 to 10 carbon atom (for example, 1 to 4 carbon atom).
Representative oxygenatedchemicals include lower straight or branched aliphatic alcohol, they unsaturated counterpart and it Nitrogen, halogen and sulfur analogs.Specially suitable oxygenatedchemicals is methanol, dimethyl ether or combinations thereof, especially methanol.
In oxygenate conversion process of the invention, comprising organic oxygen-containing compound (optionally containing a kind of or more Kind of diluent) raw material connect in the gas phase with the catalyst comprising zeolite of the present invention in the reaction region under effective process conditions Touching, to generate required alkene.Alternatively, the method can carry out in liquid phase or mixed vapor/liquid.Work as the method When carrying out in liquid phase or mixed vapour/liquid phase, catalyst and reaction condition are depended on, it is possible to create different conversion ratios and original Expect the selectivity to product.
When it is present, diluent is usually non-reactive to raw material or zeolite catalyst composition, and is commonly used in Reduce the concentration of oxygenatedchemicals in raw material.Suitable diluent include helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, Water, substantially non-reacted alkane (especially alkane, such as methane, ethane and propane), substantially non-reacted aromatics Compound and their mixture.Specially suitable diluent is water and nitrogen, particularly preferred water.Diluent can account for always into Expect 1 to 99 mole of % of mixture.
Temperature used in oxygenate conversion process can change in a wide range, such as 200 DEG C to 1000 DEG C (examples Such as, 250 DEG C to 800 DEG C, 300 DEG C to 650 DEG C or 400 DEG C to 600 DEG C).
Light olefins product will be formed at a wide range of pressures, but be not necessarily optimised quantity, including self-generated pressure and 0.1kPa to 10MPa is (for example, the pressure in 7kPa to 5MPa or 50kPa to 1MPa) range.Aforementioned pressure does not include diluent (if present), and when being related to oxygenatedchemicals and/or its mixture, the partial pressure of raw material is referred to.Under pressure Limit and the upper limit may have an adverse effect to selectivity, conversion ratio, coking rate and/or reaction rate；However, still may shape At light olefin such as ethylene.
This method should persistently be enough to generate a period of time of required olefin product.Reaction time can from a few tenths of second to A few houres etc..Reaction time is heavily dependent on reaction temperature, pressure, selected catalyst, weight (hourly) space velocity (WHSV), phase (liquid Or steam) and selected process design characteristics.
The weight (hourly) space velocity (WHSV) (WHSV) of wide scope for raw material will work in the method for the invention.WHSV be defined as into Expect the overall reaction of weight (not including diluent)/hour/Unit Weight zeolite catalyst (not including inert substance and/or filler) Volume.WHSV usually should be 0.01 to 500h-1In the range of (for example, 0.5 to 300h-1Or 1 to 200h-1)。
The actual implementation scheme of reactor system for oxygenate conversion process is have cyclic regeneration ciculation fluidized Bed reactor, is similar to Modern fluid cat cracker.The usually not preferred fixed bed of this method, because of oxygenate to olefin Conversion be high exothermic heat process, the multiple stages for needing that there is internal cooler or other cooling devices.The reaction is also Lead to high pressure drop due to generating low pressure low density gas.
AFX Framework-type zeolite of the invention can be used for being related at least one including at least one nitrogen-oxygen key compound In the catalysis process of conversion.Particularly suitable process is that zeolite of the invention is used as in selective catalytic reduction (SCR) method Catalyst and/or catalyst carrier.In the method, in reducing agent and catalyst comprising AFX Framework-type zeolite of the present invention In the presence of, selectively reduction includes nitrogen oxides (NOx) gaseous stream.Nitrogen oxides (mainly NO and NO2) be reduced into N2, while reducing agent is oxidized.When ammonia is reducing agent, N2It is also oxidation product.It is desirable that unique reaction product be water and N2Although some NH3Usually with air oxidation at NO or N2O。
In order to promote catalytic activity, another transition metal can be mixed in Zeolite support.It can choose any conjunction Suitable transition metal.In selective catalytic reduction process particularly effective transition metal include Cr, Mn, Fe, Co, Ce, Ni, One of Cu, Mo, Ru, Rh, Pd, Ag, Re, Ir and Pt or a variety of.In one embodiment, transition metal be selected from Fe and Cu.In an exemplary embodiment, transition metal is Cu.Any suitable and a effective amount of mistake can be used in the catalyst Cross metal.May include the transition metal in zeolite total amount can for 0.01 to 10 weight % (for example, 0.5 to 5 weight %, Or 1 to 2.5 weight %), the total weight based on Zeolite support.
Zeolite catalyst for nitrogen oxides reduction can be coated in suitable substrate single piece, or can shape For extrusion type catalyst, but it is preferred in catalyst coat.In one embodiment, zeolite catalyst is coated in circulation (i.e. there are many honeycomb integral catalyst carrier knots that parallel passage aisle passes axially through whole part for monolithic devices substrate Structure) or monolithic devices filter base material on such as wall-flow filter.Zeolite catalyst for this paper, which can coat, (such as to be made To wash coating ingredients) on suitable monolithic devices substrate, for example (,) metal or ceramics circulation monolithic devices substrate or filtering substrate, example Such as wall-flow filter or sintering metal or stage filter.Alternatively, zeolite can directly be synthesized on substrate and/or can be with shape At extrusion type flow type catalyst.
In addition to other non-NOxGas such as N2、O2、CO、CO2、SO2, HCl and H2Except O, the gaseous flow comprising nitrogen oxides can To include NO, NO2And N2One of O or a variety of.Air-flow can containing 1 to 10,000ppm (such as 10 to 1,000ppm or 50 to NO 500ppm).
Using containing AFX Framework-type zeolite of the present invention catalyst reduction nitrogen oxides can by any method (such as As waste gas stream) it obtains.In one embodiment, containing NOxGaseous stream be the exhaust gas from internal combustion engine.
Reducing agent can be nitrogen compound or short chain (C1-C8) hydrocarbon.Preferably, reducing agent is nitrogen compound.Suitable nitridation Closing object includes ammonia, hydrazine and ammonia precursor (for example, urea, ammonium carbonate, aminoquinoxaline, ammonium hydrogen carbonate and ammonium formate).
Gaseous stream comprising nitrogen oxides can be with 5000 to 500,000h-1(such as 10,000 to 200,000h-1) Gas hourly space velocity contacts catalyst.
The reduction of nitrogen oxides can carry out within the temperature range of 100 DEG C to 650 DEG C (for example, 250 DEG C to 600 DEG C).
The reduction of nitrogen oxides can carry out in the presence of oxygen or in the case where oxygen is not present.
Embodiment
Following illustrative embodiment is intended to be non-limiting.
Embodiment 1
Zeolite SSZ-16 is prepared according to method described in United States Patent (USP) No.4,508,837.Silicon source is sodium metasilicate, silicon source It is aluminum sulfate, structure directing agent is Isosorbide-5-Nitrae-two (1- azabicyclo [2.2.2] octane) butyl dibromide.
The powder X-ray RD of products therefrom is the feature of SSZ-16.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 12.
Embodiment 2
Zeolite SSZ-16 is prepared according to method described in United States Patent (USP) No.5,194,235.To being added in PTFE glasss 1.75g sodium silicate solution, 0.18g LZ-210 zeolite (NH4-USY,SiO2/Al2O3Molar ratio=15), 3.77g 1N NaOH, 1.56g deionized water and bis- [4- azepine -1- azabicyclo [2.2.2] octane] dibromos of 0.49g1,1'- (butane -1,4- diyl) Compound (DABCO-C4- DABCO dibromide).Mixture is stirred with scraper so that it is uniform.With molar ratio computing, reaction mixture It is final composition it is as follows:
SiO2/Al2O3 72
Q/SiO2 0.15
NaOH/SiO2 0.9
H2O/SiO2 35
PTFE glasss are covered and is sealed in stainless steel autoclave.Then the autoclave is fixed on and is heated to 140 DEG C Baking oven in overturning (43rpm) 14 days.By filtering the recycling solid product from cooling reactor and being washed with deionized. It is dried overnight the solid of recycling at 95 DEG C in an oven.
The powder X-ray RD of products therefrom is the feature of SSZ-16.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 9.5.
Embodiment 3
Embodiment 2 is repeated, the difference is that the final composition of reaction mixture, as follows with molar ratio computing:
SiO2/Al2O3 35
Q/SiO2 0.15
NaOH/SiO2 1.0
H2O/SiO2 33.8
The powder xrd pattern of products therefrom is the feature of SSZ-16.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 7.1.
Embodiment 4
AFX Framework-type zeolite is prepared according to method described in United States Patent (USP) No.8,562,942.To being added in PTFE glasss 0.19g CBV100Na-Y zeolite (Zeolyst International, SiO2/Al2O3Molar ratio=5.1), 1g 1N NaOH, Bis- (1- adamantyl) the imidazolium hydroxide aqueous solutions (0.58mmole OH/g solution) of 3.47g 1,3- and 1.61g water.So Afterwards, 0.62g is addedM-5 pyrogenic silica (CabotCorporation).It is stirred with scraper Object is so that it is uniform.With molar ratio computing, the final composition of reaction mixture is as follows:
SiO2/Al2O3 34
Q/SiO2 0.20
NaOH/SiO2 0.158
H2O/SiO2 30
PTFE glasss are covered and is sealed in stainless steel autoclave.Then the autoclave is fixed on and is heated to 150 DEG C Baking oven in overturning (43rpm) 21 days.By filtering the recycling solid product from cooling reactor and being washed with deionized. It is dried overnight the solid of recycling at 95 DEG C in an oven.
The powder X-ray RD of products therefrom is the feature of AFX framework type material.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 28.
Embodiment 5
To 0.62g is added in PTFE glasssM-5 pyrogenic silica (Cabot Corporation), 0.18g LZ-210 zeolite, bis- (1- adamantyl) the imidazolium hydroxide aqueous solutions of 1.0g 1N NaOH and 3.47g 1,3- (0.58mmol OH/g solution).Mixture is stirred with scraper so that it is uniform.With molar ratio computing, final group of reaction mixture At as follows:
SiO2/Al2O3 90
Q/SiO2 0.17
NaOH/SiO2 0.08
H2O/SiO2 25
PTFE glasss are covered and is sealed in stainless steel autoclave.Then the autoclave is fixed on and is heated to 150 DEG C Baking oven in overturning (43rpm) 21 days.By filtering the recycling solid product from cooling reactor and being washed with deionized. It is dried overnight the solid of recycling at 95 DEG C in an oven.
The powder X-ray RD of products therefrom is the feature of AFX framework type material.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 66.
Embodiment 6
To 0.62g is added in PTFE glasssM-5 pyrogenic silica (Cabot Corporation), 0.25g LZ-210 zeolite, bis- (1- adamantyl) the imidazolium hydroxide aqueous solutions of 1.2g 1N NaOH and 3.47g 1,3- (0.58mmol OH/g solution).Mixture is stirred with scraper so that it is uniform.With molar ratio computing, final group of reaction mixture At as follows:
SiO2/Al2O3 70
Q/SiO2 0.16
NaOH/SiO2 0.09
H2O/SiO2 24
PTFE glasss are covered and is sealed in stainless steel autoclave.Then the autoclave is fixed on and is heated to 150 DEG C Baking oven in overturning (43rpm) 21 days.By filtering the recycling solid product from cooling reactor and being washed with deionized. It is dried overnight the solid of recycling at 95 DEG C in an oven.
The powder X-ray RD of products therefrom is the feature of AFX framework type material.
By ICP determination of elemental analysis, the SiO of original sample product after synthesis2/Al2O3Molar ratio is 53.

Claims (10)

1. a kind of AFX Framework-type zeolite, the zeolite under form, has the composition including following molar relationship after its calcining:
Al2O3:(n)SiO2
Wherein the value of n is greater than 50 to 100.
2. AFX Framework-type zeolite according to claim 1, wherein the value of n is greater than 50 to 80.
3. AFX Framework-type zeolite according to claim 1, wherein the value of n is 52 to 70.
4. a kind of AFX Framework-type zeolite, the zeolite after its synthesis as former state and under anhydrous form, have with molar ratio computing as Lower composition:
SiO2/Al2O3 > 50 to 100 Q/SiO2 > 0 to 0.1 M/SiO2 > 0 to 0.1
Wherein Q includes bis- (1- adamantyl) glyoxaline cations of 1,3-, and M is the metal selected from periodic table the 1st race and the 2nd race.
5. AFX Framework-type zeolite according to claim 4, wherein SiO2/Al2O3Molar ratio be greater than 50 to 80.
6. AFX Framework-type zeolite according to claim 4, wherein SiO2/Al2O3Molar ratio be 52 to 70.
7. a kind of method of AFX Framework-type zeolite described in synthesis claim 4, which comprises
(a) reaction mixture including following substance is provided:
(1) include FAU Framework-type zeolite silicon source；
(2) individual silicon source；
(3) it is selected from source at least one metal (M) of the 1st race of the periodic table of elements and the 2nd race；
(4) source 1,3- bis- (1- adamantyls) glyoxaline cation (Q)；
(5) hydroxide ion；With
(6) water；And
(b) reaction mixture is made to be subjected to being enough to be formed the crystallization condition of AFX Framework-type zeolite crystal,
Wherein the reaction mixture is had and is formed with the following of molar ratio computing:
SiO2/Al2O3 > 50 to 100 M/SiO2 0.05 to 0.25 Q/SiO2 0.10 to 0.30 OH/SiO2 0.15 to 0.55 H2O/SiO2 15 to 60
。
8. according to the method described in claim 7, wherein the crystallization condition includes 125 DEG C to 200 DEG C of temperature.
9. a kind of method for converting converted product for the raw material comprising organic compound, the method includes in organic compound The step of contacting raw material and catalyst under conversion condition, the catalyst include AFX Framework-type zeolite described in claim 1 Active form.
10. a kind of selective reducing nitrogen oxide (NOx) method, the method includes making containing NOxAir-flow and include right It is required that the catalyst of 1 zeolite contacts.
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